High-performance and flexible poly(pyrroloneimide)s (PPyIs) were firstly prepared by the reaction of dianhydrideswith an unsymmetric phosphinated triamine, 1-(3,4-diaminophenyl)-1-(4-aminophenyl)-1-(6-oxido-6H -dibenz <c,e><1,2> oxaphosphorin-6-yl)ethane (1), which was prepared by afacile, one-pot procedure from the reaction DOPO, 4-aminoacetophenonein excess o-phenylenediamine in the presence ofp-toluenesulfonic acid. Thermal properties of the resulting PPyIswere evaluated and compared with those of phosphinated polyimideswith a similar structure. All of the prepared PPyIs films aretough and creasable. They display higher Tg (374–412 C), lowercoefficient of thermal expansion (34–46 ppm/ C), and better thermalstability (Td 5 wt %: 456–477 C, 800 C char yield: 59–63%)than analogous phosphinated polyimides
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